CN102046695A - Methods of controlling molecular weight distribution of polymers and compositions thereof - Google Patents

Methods of controlling molecular weight distribution of polymers and compositions thereof Download PDF

Info

Publication number
CN102046695A
CN102046695A CN2009801198587A CN200980119858A CN102046695A CN 102046695 A CN102046695 A CN 102046695A CN 2009801198587 A CN2009801198587 A CN 2009801198587A CN 200980119858 A CN200980119858 A CN 200980119858A CN 102046695 A CN102046695 A CN 102046695A
Authority
CN
China
Prior art keywords
reaction
product
reactive component
catalyst
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2009801198587A
Other languages
Chinese (zh)
Other versions
CN102046695B (en
Inventor
S·D·艾伦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saudi Aramco Technologies Co
Original Assignee
Novomer Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novomer Inc filed Critical Novomer Inc
Priority to CN201310308300.1A priority Critical patent/CN103626983B/en
Publication of CN102046695A publication Critical patent/CN102046695A/en
Application granted granted Critical
Publication of CN102046695B publication Critical patent/CN102046695B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

A catalyst, co-catalyst, and/or chain transfer agent is added at a time after initiation of an addition polymerization reaction to produce a polymer product with a widened molecular weight distribution relative to having all of the components in the original reaction mixture. The catalyst, co-catalyst, or chain transfer agent may be added discretely or continuously to the reaction to produce a product with a bimodal, trimodal, or other broadened molecular weight distribution.

Description

The method of controlling polymers and composition molecular weight distribution thereof
Association area
The application requires to enjoy the rights and interests of one or more inventions, and it is that its applying date is on May 29th, 2008 in 12/129,106 the United States Patent (USP) that its content is disclosed in application number, and denomination of invention is " method of controlling polymers and composition molecular weight distribution thereof ".This application is combined in this by reference.
Technical field
The present invention relates to the addition polymerization field.Further, the present invention relates to control the method for the molecular weight of polyaddition product.
Background technology
Addition polymerization also is called addition polymerization and chain growth polymerization, and it progressively adds on the polymer chain that is increasing by monomeric unit and carries out.Addition polymerization is carried out with three remarkable different steps.Each chain at first is initiated, and increases then, stops at last.Owing to monomeric unit progressively addition carry out polyreaction, therefore under set initial reaction condition, suppose that the molecular-weight average of polymer chain is linear growth with the reaction times when having superfluous monomer.
The polymkeric substance that is formed by addition polymerization includes but not limited to: polyolefine, polycarbonate, polyester and polyethers.The specific examples of addition polymer includes but not limited to, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), polyacrylonitrile, polyvinyl acetate (PVA), polymethylmethacrylate (PMMA), polyvinyl acetate (PVA), polytetrafluoroethylene (PTFE), poly-plutonium carbonate hexene ester (PCHC), polymerized thylene carbonate ethyl ester (PEC), poly (propylene carbonate) (PPC) and poly(propylene oxide) (PPO).
Coates and Moore (the 43rd rolls up for Angew.Chem., Int.Ed., and the 6618-6639 page or leaf 2004, is combined in this by reference) have commented the copolymerization catalyst that is used for carbonic acid gas and epoxide addition polymerization.These metal-based catalyst include but not limited to: aluminium-, manganese-, chromium-, cobalt-, yttrium-, zinc-, cadmium-and nickel-catalyst based.It all is combined in this people such as Qin (Angew.Chem. by reference, Int.Ed., 42, the 5484-5487 page or leaf, 2003), people (J.Am.Chem.Soc., 127 such as Cohen, the 10869-10878 page or leaf, 2005) and the U.S. Pat 7,304,172 of authorizing people such as Coates disclosed and be used for the cobalt catalyst that oxirane and carbon dioxide copolymerization close.Be combined in this people such as Coates (Angew.Chem., Int., Ed. by reference, 43, the 6618-6639 pages or leaves, 2004) and the U.S. Pat 6 of authorizing people such as Coates, 133,402 have disclosed and have been used for zinc-base and other metal-based catalyst that oxirane and carbon dioxide copolymerization close.
In polyaddition reaction, one or more promotors can use jointly with catalyzer, compare with the catalyzer of independent use, and it can be accelerated polymerization velocity and allow to reduce reaction pressure or temperature potentially.Promotor can improve the stereoselectivity or the regioselectivity of polyreaction simultaneously.(US 7 for people such as Coates, 304,172) disclosed two (triphenylphosphine) chlorimide (iminium), two (triphenylphosphine) pentafluorobenzoic acid imines, 4-phenyl phosphonium bromide, tetraphenyl phosphonium chloride, tetrabutylammonium chloride, triethylamine and trioctylamine and used jointly, come the copolymerization of catalysis oxirane and carbonic acid gas as promotor and cobalt catalyst.
The reversible chain-transfer agent can make the molecular-weight average that is used for reducing product jointly with catalyzer, can to polyaddition reaction remarkably influenced not arranged in addition.(US 7 for people such as Coates, 304,172) carboxylic acid such as pentafluorobenzoic acid, pure form have been disclosed as methyl alcohol, dicarboxylic acid, glycol, polyprotonic acid, polyvalent alcohol and their deprotonation, such as pentafluorobenzoic acid sodium, it can be used as the reversible chain-transfer agent and uses in the copolymerization of propylene oxide and carbonic acid gas with cobalt catalyst.
Summary of the invention
Catalyzer, promotor and/or chain-transfer agent are caused the back at polyaddition reaction add, can make a kind of polymkeric substance, this polymer phase for all components all in the initial reaction mixture and have the molecular weight distribution of widening for the polymkeric substance that obtains.Described catalyzer, promotor or chain-transfer agent can be discontinuously or are added continuously in the reaction, have the product of bimodal distribution, the distribution of three peaks or other broadening molecular weight distribution with generation.
In first embodiment of the present invention, the molecular weight distribution of described method may command polyaddition reaction product.Described method is included in initiation time initiation polyaddition reaction and at least one reaction times after the initiation time at least a reactive component is added in the reaction.Described reactive component is selected from least a catalyzer, at least a promotor, at least a reversible chain-transfer agent and their arbitrary combination.
In second embodiment of the present invention, the molecular weight distribution of the polycarbonate products of described method may command polyaddition reaction.Described method is included in initiation time initiation polyaddition reaction and at least one reaction times after the described initiation time at least a reactive component is added in the reaction.
In the 3rd embodiment of the present invention, described method can make a kind of polyaddition reaction product that predetermined molecular weight distributes that has.Described method comprises that the starting condition of determining described reaction and at least one velocity constant of utilizing reaction calculate at least a add-on that adds at least a reactive component in the reaction at least one reaction times after the initiation time.Described method also is included in the initiation reaction and in the reaction times reactive component being added in the reaction under starting condition of initiation time.Described reactive component is selected from: at least a catalyzer, at least a promotor, at least a reversible chain-transfer agent and their arbitrary combination.
In the 4th embodiment of the present invention, described polymeric articles comprises the polymeric articles of the first addition polymer product that comprises single batchwise polymerization.The described first addition polymer product has the molecular weight distribution that is different from the second addition polymer product, and the described second addition polymer product is to produce by the total overall reaction component that adds the second addition polymer product when the polyreaction of preparation second addition polymer begins or finishes.
Description of drawings
Figure 1 shows that the method for synthetic polymer in the embodiment of the present invention.
Embodiment
The addition polymerization of Shi Yonging herein comprises that the mode with progressively of any existence is added to monomeric unit respectively and has on the polymer chain that increases, and makes the molecular-weight average of product roughly be the polyreaction near linear growth in time under given reaction conditions.
Addition polymerization used in the method for the present invention includes but not limited to: synthesis of polyolefins, polycarbonate, the addition polymerization of polyhydroxyalkanoatefrom and polyethers, the example comprise polyethylene (PE), polypropylene (PP), polybutene, polyisobutene, polyvinyl chloride (PVC), polystyrene (PS), polyacrylonitrile, polyvinyl acetate (PVA) (PVA), polymethylmethacrylate (PMMA), polyvinyl acetate (PVA), polytetrafluoroethylene (PTFE), poly-plutonium carbonate hexene ester (PCHC), polymerized thylene carbonate ethyl ester (PEC), poly (propylene carbonate) (PPC) and poly(propylene oxide) (PPO).Though method of the present invention can be used for implementing any addition polymerization, in certain embodiments, described polymerization is the copolymerization of carbonic acid gas and epoxide.In one embodiment, described polymerization is the copolymerization of propylene oxide and carbonic acid gas.
The catalyzer of Shi Yonging comprises herein anyly can increase the polymeric speed of response in chemical reaction, and does not have the chemical part that consumes in described chemical reaction.The catalyzer that uses in the inventive method comprise but be not limited to aluminium-, manganese-, chromium-, cobalt-, yttrium, zinc, cadmium-and Ni-based-catalyzer.Though method of the present invention can be used any catalyzer that is used for addition polymerization, in some specific embodiment, described catalyzer is the metal-based catalyst that is used for carbonic acid gas and epoxide copolymerization.In one embodiment, described catalyzer is to be used for the cobalt-base catalyst that epoxide and carbon dioxide copolymerization close.In another embodiment, described catalyzer is to be used for the chromium-based catalysts that epoxide and carbon dioxide copolymerization close.In certain embodiments, described catalyzer is to be used for the zinc-base catalyzer that epoxide and carbon dioxide copolymerization close.
The promotor of Shi Yonging comprises any chemical part herein, and when itself and catalyzer were used jointly, with respect to the polymerization velocity that does not use promotor, it can increase the speed of polyreaction.The promotor that uses in the method for the present invention includes but not limited to, amine, ammonium salt, phosphonium salt and arsenic salt, its specific examples comprise that two (triphenylphosphine) chlorimide (PPN-Cl), two (triphenylphosphines) five fluoridize phenylformic acid imines, 4-phenyl phosphonium bromide, tetraphenyl phosphonium chloride, tetra-n-butyl ammonia chloride, triethylamine, trioctylamine, Dimethylamino pyridine (DMAP), Methylimidazole, 3-pyridone and dimethylamino quinoline (DMAQ).Though method of the present invention can be used any addition polymerization promotor that is used for, in certain embodiments, described promotor is the promotor that is used for the copolymerization of carbonic acid gas and epoxide.In one embodiment, described promotor is to be used for the PPN-Cl that propylene oxide and carbon dioxide copolymerization close.
The reversible chain-transfer agent of Shi Yonging comprises any chemical part that can make polymer chain reversibly be connected to or break away from catalyzer herein, and wherein when catalyzer was not on polymer chain, polymer chain just no longer increased.The concentration that increases the reversible chain-transfer agent can reduce the molecular-weight average of synthetic polymer by the number that increases living polymer chains.If the speed of chain transfer is faster with respect to polymerization velocity, so whole polymer chains will increase with identical V-bar.The reversible chain-transfer agent that method of the present invention is used can change with the type of the polyreaction that relates to.The reversible chain-transfer agent that uses in the inventive method includes, but are not limited to carboxylic acid, alcohol, dicarboxylic acid, glycol, polyprotonic acid, polyvalent alcohol and their deprotonation form and mercaptan, iodate perfluoro alkane, two iodate perfluoro alkanes, pentane, propane and butane.Though method of the present invention can be used from any polyaddition reaction with any reversible chain-transfer agent one, in the embodiment of the copolymerization of some carbonic acid gas and epoxide, described reversible chain-transfer agent is an alcohol (comprising polyvalent alcohol).In the embodiment that a propylene oxide and carbon dioxide copolymerization close, described reversible chain-transfer agent is an ethylene glycol.
The chain terminator of Shi Yonging also is called the irreversible chain transfer agent herein, and it comprises any chemical part that makes polymer chain forever break away from catalyzer, and wherein when catalyzer was not on polymer chain, polymer chain no longer increased.The chain terminator that uses in the inventive method changes with the type of the polyreaction that relates to.The concentration that increases chain terminator can reduce the molecular-weight average of synthetic polymer.The chain terminator that uses in the inventive method includes but not limited to hydrogen, halogenated alkane and bromotoluene.
The chain-transfer agent of Shi Yonging comprises any chemical part that can make polymer chain be connected to and/or break away from catalyzer herein, and wherein when catalyzer was not on polymer chain, polymer chain no longer increased.Chain-transfer agent includes but not limited to reversible chain-transfer agent and chain terminator.
The reactive component of Shi Yonging comprises any chemical part that can change the molecular weight distribution of polyaddition reaction product herein.The reactive component that uses in the method for the present invention includes but not limited to catalyzer, promotor and chain-transfer agent.
When reagent only begins to add fashionable in polyreaction, polyaddition reaction is compared generation with condensation polymerization the finished product have relative narrow molecular weight distribution.Have than the polymkeric substance of wide molecular weight distribution and wish in some applications.For example, the part that has higher molecu lar weight component and lower molecular weight component simultaneously can produce not only having workability but also the polymeric articles of intensity being arranged of expectation, and can not be obtained the combination of above-mentioned performance by the product of narrow molecular weight distributions.
In the method for the invention, at least a reactive component is added after initiation reaction in the polyaddition reaction, have the polymeric articles of wider molecular weight distribution with generation.Any combination of at least a reactive component can be added in the described reaction, it comprises multiple catalyzer, multiple promotor and/or multiple chain-transfer agent.Described reactive component can be added in one or more discrete times and/or above the speed of one or more time cycles with constant or variation.One or more described reactive components can add with any predetermined consumption or any predetermined speed any predetermined (a plurality of) time and/or (a plurality of) time cycle in reaction process, produce polymeric articles.Perhaps, described time, time cycle and consumption, speed can determine in the process of described reaction.Described reactive component can be in a discrete step, in a plurality of identical or different discontinuous steps, add in the described reaction, or add in the described reaction with fixed or changed speed in one or more time cycles continuously with fixed or changed interval.Reactive component preferably adds under mixing, to disperse initiate raw material.In one embodiment, the discontinuous time of described reactive component after the reaction beginning is added, make product have bimodal molecular weight and distribute.In another embodiment, two the discontinuous times of described reactive component after the reaction beginning are added, make product have three peak type molecular weight distribution.
In one embodiment, described polymerization is addition polymerization, and wherein reactive component is selected from catalyzer, promotor and reversible chain-transfer agent.
In another embodiment, described polymerization is the addition polymerization that forms polycarbonate, and wherein reactive component is selected from catalyzer, promotor and reversible chain-transfer agent.
Preferably method of the present invention being used for batchwise polymerization carries out, wherein at least some polymer chains increase in entire reaction course always, rather than successive polymerization, wherein periodically be added to chain terminator in the reaction, stop the polymer chain that all increases with predetermined molecular-weight average, and begin to increase new chain.
Figure 1 shows that the method for the synthetic polyaddition reaction product of one embodiment of the invention.Use a certain amount of catalyzer, promotor, chain-transfer agent and monomer to cause 10 reactions.Certain time after the initiation time, exist inquiry 12 to determine whether one or more reactive components are added in the described reaction.If add one or more reactive components, exist inquiry 14 to determine whether to add all reactive components so at one discrete batch.If add whole reactive components, so described reactive component is added 16 in described reaction mixture at one discontinuous batch.There is another inquiry 12 to determine whether to add one or more reactive components in described reaction after this.If in for some time, add reactive component in a continuous manner, so just begin to add 18 in the forward time, stop 20 in the time after a while then.If do not add reactive component, exist inquiry 22 to determine whether to stop described reaction so.Described reaction can be terminated 24 or continue subsequently.In another embodiment shown in Figure 1, the interpolation of differential responses component can be carried out with overlapping each other.For example, during a continuous interpolation catalyzer and promotor, chain-transfer agent can discontinuous or continuous interpolation.The whenever interpolation of monomer in also can be during polyreaction is though monomer preferably only added before initiation reaction.
Cause time of 10 in reaction, can be with any amount, do not comprise any or all of catalyzer, promotor and chain-transfer agent and combination of monomers, and begin reaction.
In one embodiment of the invention, the joining day of one or more reactive components, speed and add-on can distribute according to the desired molecule amount of speed of response under the known reaction conditions and predetermined final polymeric articles and pre-determine.
In another embodiment, monitoring reaction, and determine joining day, speed and the add-on of one or more reactive components by the progress of monitoring reaction.
Than the total overall reaction raw material is all added reactor in the initial stage of polyreaction, the add-on/adding speed of control reaction conditions and one or more reactive components and time can be realized bigger control and the handiness to the finished product molecular weight distribution of polyaddition reaction.
Compare with respect to beginning or the resulting addition polymer product of ending phase adding total overall reaction component in polyreaction, the addition polymer product of the single batchwise polymerization in another embodiment of the invention has different molecular weight distribution.
Following embodiment will be used for setting forth explanation rather than limit principle of the present invention.In following examples, M represents a kind of unitary molecular weight, R 0Unitary adding speed when being illustrated in the reaction beginning, C xAnd r xExpression molal unit rather than mass unit.For the single component polymerization, described unit is meant monomer molecule.For copolymerization, described unit is meant the first monomeric molecule and the second monomeric molecule.Below among the embodiment, when existing or add promotor, always exist or the interpolation promotor according to predetermined optimal or approaching optimal ratio with catalyzer, though promotor can not add with catalyzer or add with non-optimal ratio, to change molecular weight distribution, this also belongs in the spirit of the present invention.For the ease of the calculating among the following embodiment, suppose and think and be reflected at time t NDo not finish, although reaction time of carrying out may be longer than and be finished the time that reaction expects and also belong to spirit of the present invention before.
Embodiment 1
At initial time t 0, reaction comprises C 0The catalyzer of consumption and excessive monomer.At time t after a while 1, with additional quantity C 1Catalyzer add in the described reaction.At time t after a while N, stop described reaction.The product of described reaction has bimodal molecular weight and distributes, wherein the P of first part 1Has about C 0/ (C 0+ C 1) molar fraction, and have about M (1+R 0(t N-t 0)) molecular-weight average, second section P 2Has about C 1/ (C 0+ C 1) molar fraction, and have about M (1+R 0(t N-t 1)) molecular-weight average.
Embodiment 2
At initial time t 0, reaction comprises C 0The catalyzer of consumption and excessive monomer.At time t after a while 1, will measure A 1The reversible chain-transfer agent add in the reaction.At time t after a while N, termination reaction.The product of described reaction has bimodal molecular weight and distributes, wherein the P of first part 1Has about C 0/ (C 0+ A 1) molar fraction, and have about M (1+R 0(t 1-t 0The molecular-weight average of)+X), second section P 2Has about A 1/ (C 0+ A 1) molar fraction, and have the molecular-weight average of about M (1+X), wherein, X=R 0(C 0/ (C 0+ A 1)) (t N-t 1), suppose that the speed of chain transfer is faster with respect to polymerization velocity.
Embodiment 3
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption and excessive monomer.At time t after a while 1, with extra consumption C 1Catalyzer and B 1Promotor add in the reaction wherein ratio of both consumptions and C to 0: B 0Identical.At time t after a while N, stop described reaction.The product of described reaction has bimodal molecular weight and distributes, wherein the P of first part 1Has approximately (C 0+ B 0)/(C 0+ B 0+ C 1+ B 1) molar fraction, and have about M (1+R 0(t N-t 0)) molecular-weight average, second section P 2Has approximately (C 1+ B 1)/(C 0+ B 0+ C 1+ B 1) molar fraction, and have about M (1+R 0(t N-t 1)) molecular-weight average.
Embodiment 4
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption and excessive monomer.At time t after a while 1, with consumption A 1The reversible chain-transfer agent add in the reaction.At time t after a while N, stop described reaction.The product of described reaction has bimodal molecular weight and distributes the P of first part 1Has approximately (C 0+ B 0)/(C 0+ B 0+ A 1) molar fraction, and have about M (1+R 0(t 1-t 0The molecular-weight average of)+X), second section P 2Has about A 1/ (C 0+ B 0+ A 1) molar fraction, it approximately has the molecular-weight average of M (1+X), wherein, X=R 0((C 0+ B 0)/(C 0+ B 0+ A 1)) (t N-t 1), suppose that the speed of chain transfer is faster with respect to polymerization velocity.
Embodiment 5
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption, A 0The reversible chain-transfer agent of consumption and excessive monomer.At time t after a while 1, with C 1The catalyzer of consumption, B 1The promotor of consumption, A 1The reversible chain-transfer agent of consumption adds in the reaction.At time t after a while N, stop described reaction.The product of described reaction has bimodal molecular weight and distributes the P of first part 1Has approximately (C 0+ B 0+ A 0)/(C 0+ B 0+ A 0+ C 1+ B 1+ A 1) molar fraction, and have about M (1+R 0(t 1-t 0The molecular-weight average of)+X), second section P 2Has approximately (C 1+ B 1+ A 1)/(C 0+ B 0+ A 0+ C 1+ B 1+ A 1) molar fraction, and have the molecular-weight average of about M (1+X), wherein, X=R 0(((C 0+ B 0+ C 1+ B 1)/(C 0+ B 0+ A 0+ C 1+ B 1+ A 1))/((C 0+ B 0)/(C 0+ B 0+ A 0))) (t N-t 1), suppose that the speed of chain transfer is faster with respect to polymerization velocity.
Embodiment 6
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption, A 0The reversible chain-transfer agent of consumption and excessive monomer.At time t after a while 1, with C 1The catalyzer of consumption, B 1The promotor of consumption, A 1The reversible chain-transfer agent of consumption adds in the reaction.At the second time t after a while 2, with C 2The catalyzer of consumption, B 2The promotor of consumption, A 2The reversible chain-transfer agent of consumption adds in the reaction.At time t after a while N, stop described reaction.Reaction product has three peak type molecular weight distribution, the P of first part 1Has approximately (C 0+ B 0+ A 0)/(C 0+ B 0+ A 0+ C 1+ B 1+ A 1+ C 2+ B 2+ A 2) molar fraction, and have about M (1+R 0(t 1-t 0The molar fraction of)+X+Y), second section P 2Has approximately (C 1+ B 1+ A 1)/(C 0+ B 0+ A 0+ C 1+ B 1+ A 1+ C 2+ B 2+ A 2) molar fraction, and have the molar fraction of about M (1+X+Y), third part P 3Has approximately (C 2+ B 2+ A 2)/(C 0+ B 0+ A 0+ C 1+ B 1+ A 1+ C 2+ B 2+ A 2) molar fraction, and have the molar fraction of about M (1+Y), wherein, X=R 0(((C 0+ B 0+ C 1+ B 1)/(C 0+ B 0+ A 0+ C 1+ B 1+ A 1))/((C 0+ B 0)/(C 0+ B 0+ A 0))) (t 2-t 1), Y=R 0(((C 0+ B 0+ C 1+ B 1+ C 2+ B 2)/(C 0+ B 0+ A 0+ C 1+ B 1+ A 1+ C 2+ B 2+ A 2))/((C 0+ B 0)/(C 0+ B 0+ A 0))) (t N-t 2), suppose that the relative polymerization velocity of speed of chain transfer is faster.
Embodiment 7
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption, A 0The reversible chain-transfer agent of consumption and excessive monomer.At time (t after a while 1, t 2..., t N-2And t N-1), with consumption (C 1, C 2..., C N-2And C N-1) catalyzer, consumption (B 1, B 2..., B N-2And B N-1) promotor and consumption (A 1, A 2..., A N-2And A N-1) the reversible chain-transfer agent add in the reaction.At time t after a while N, termination reaction.Reaction product has n-peak type molecular weight distribution, for each part P i, and have approximately (C i+ B i+ A i)/(∑ C+ ∑ B+ ∑ A) molar fraction, i=0 is to n-1, and has about M (1+ ∑ (R 0(((C 1+ B 1)/(∑ C+ ∑ B+ ∑ A))/((C 0+ B 0)/(C 0+ B 0+ A 0))) (t I+1-t 1)) molecular-weight average, suppose that the speed of chain transfer is faster with respect to polymerization velocity.
Embodiment 8
At initial time t 0, reaction comprises C 0The catalyzer of consumption and excessive monomer.At time t after a while 1, be A with consumption 1The reversible chain-transfer agent add in the reaction.At a time t after a while 2, with D 2The chain terminator of consumption adds in the reaction, wherein D 2Less than C 0+ A 1At time t after a while N, stop described reaction.Reaction product has three peak type molecular weight distribution, the P of first part 1Has about C 0(C 0+ A 1-D 2)/(C 0+ A 1) 2Molar fraction, and have about M (1+R 0(t 1-t 0The molecular-weight average of)+X), second section P 2Has about A 1(C 0+ A 1-D 2)/(C 0+ A 1) 2Molar fraction, and have the molecular-weight average of about M (1+X), third part P 3Has about D 2/ (C 0+ A 1) molar fraction, and have the molecular-weight average of about M (1+Y), wherein, X=R 0(C 0/ (C 0+ A 1)) (t N-t 1), and Y=R 0(C 0/ (C 0+ A 1)) (t N-t 2), suppose that chain transfer and terminated speed are faster with respect to polymerization velocity.
Embodiment 9
At initial time t 0, reaction comprises C 0The catalyzer of consumption and excessive monomer.At t 1To t 2Time cycle in, with extra catalyzer with r cConstant speed be added continuously in the reaction.At time t after a while N, stop described reaction.Reaction product has the molecular weight distribution that broadens.The molecular weight distribution of described reaction product has about C 0/ (C 0+ r C(t 2-t 1)) the P of first part of molar fraction 1, and have about M (1+R 0(t N-t 0)) molecular-weight average, remainder P 2Have approximately be with the mole basis divide from M (1+R 0(t N-t 2)) to M (1+R 0(t N-t 1)) molecular-weight average.
Embodiment 10
At initial time t 0, reaction comprises C 0The catalyzer of consumption and excessive monomer.At time cycle t 1To t 2, with the reversible chain-transfer agent with r AConstant speed be added continuously in the reaction.At time t after a while N, stop described reaction.Reaction product has the molecular weight distribution that broadens.The molecular weight distribution of reaction product has about C 0/ (C 0+ r A(t 2-t 1)) the P of first part of molar fraction 1, and have about M (1+R 0(t 1-t 0The molecular-weight average of)+X+Y), remainder P 2Have approximately is the molecular-weight average from M (1+Y) to M (1+X+Y) that the basis is divided, wherein X=R with the mole 0∫ (C 0/ (C 0+ r A(t-t 1))) dt, from t 1To t 2, Y=R 0(C 0/ (C 0+ r A(t 2-t 1))) (t N-t 2).
Embodiment 11
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption and excessive monomer.At time cycle t 1To t 2, be respectively with constant speed r with extra catalyzer and promotor CAnd r BAdd to continuously in the reaction, wherein r C: r B=C 0: B 0At time t after a while N, stop described reaction.Reaction product has the molecular weight distribution that broadens.The molecular-weight average of described reaction product distributes and has approximately (C 0+ B 0)/(C 0+ r A(t 2-t 1)+B 0+ r B(t 2-t 1)) the P of first part of molar fraction 1, and have about M (1+R 0(t N-t 0)) molecular-weight average, remainder P 2Have approximately be with the mole basis divide from M (1+R 0(t N-t 2)) to M (1+R 0(t N-t 1)) molecular-weight average.
Embodiment 12
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption and excessive monomer.At t 1To t 2Time cycle in, the reversible chain-transfer agent is with r AConstant speed be added continuously in the reaction.At time t after a while N, termination reaction.Reaction product has the molecular weight distribution that broadens.The molecular weight distribution of described reaction product has approximately (C 0+ B 0)/(C 0+ B 0+ r A(t 2-t 1)) the P of first part of molar fraction 1, and have about M (1+R 0(t 1-t 0The molecular-weight average of)+X+Y), remainder P 2Have is the molecular-weight average from M (1+Y) to M (1+X+Y) that the basis separates, wherein X=R with the mole approximately 0∫ ((C 0+ B 0)/(C 0+ B 0+ r A(t-t 1))) dt, from t 1To t 2, and Y=R 0((C 0+ B 0)/(C 0+ B 0+ r A(t 2-t 1))) (t N-t 2).
Embodiment 13
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption, A 0The reversible chain-transfer agent of consumption and excessive monomer.At time cycle t 1To t 2, with extra catalyzer, promotor and reversible chain-transfer agent respectively with constant speed r C, r BAnd r AAdd in the reaction continuously.At time t after a while N, stop described reaction.Reaction product has the molecular weight distribution that broadens.The molecular weight distribution of the product of described reaction has molar fraction and is approximately (C 0+ B 0+ A 0)/(C 0+ B 0+ A 0+ (r A+ r B+ r C) (t 2-t 1)) the P of first part 1, and have about M (1+R 0(t 1-t 0The molecular-weight average of)+X+Y), remainder P 2Has the molecular-weight average that approximately separates to M (1+X+Y), wherein X=R from M (1+Y) 0∫ ((C 0+ B 0+ A 0)/(C 0+ B 0+ A 0+ (r A+ r B+ r C) (t-t 1))) dt, from t 1To t 2, and Y=R 0((C 0+ B 0+ A 0)/(C 0+ B 0+ A 0+ (r A+ r B+ r C) (t 2-t 1))) (t N-t 2).
Embodiment 14
At initial time t 0, reaction comprises excessive monomer.At time cycle t 0To t 1, with catalyzer, promotor and reversible chain-transfer agent respectively with constant speed r C, r BAnd r ABe added continuously in the reaction.At time t after a while N, stop described reaction.Reaction product has the molecular weight distribution that broadens.Work as catalyzer: promotor: the ratio of reversible chain-transfer agent is r C: r B: r A, when R referred to the interpolation speed of monomeric unit, the molecular weight distribution of described reaction product had approximately from M (1+R (t N-t 1)) to M (1+R (t N-t 0)) the average molecular weight range that separates.
Embodiment 15
At initial time t 0, reaction comprises C 0The catalyzer of consumption, B 0The promotor of consumption, A 0The reversible chain-transfer agent of consumption and excessive monomer.At time interval (t after a while 1To t 2, t 3To t 4..., t N-4To t N-3And t N-2To t N-1), with catalyzer, promotor and reversible chain-transfer agent respectively with r C, 1, r C, 2..., r C, (N-3)/2And r C, (N-1)/2, r B, 1, r B, 2...., r B, (N-3)/2, r B, (N-1)/2And r A, 1, r A, 2..., r A, (N-3)/2, r A, (N-1)/2Continuously in described reaction.At time t after a while N, stop described reaction.Described reaction product has the molecular weight distribution that broadens.The molecular weight distribution of reaction product has approximately (C 0+ B 0+ A 0)/(C 0+ ∑ r C, i(t 2i-t 2i-1)+B 0+ ∑ r B, i(t 2i-t 2i-1)+A 0+ ∑ r A, I(t 2i-t 2i-1)) the P of first part of molar fraction 1, and have about M (1+R 0(t 1-t 0)+∑ X i+ ∑ Y i) molecular-weight average, wherein i=1 is to (N-1)/2, and the P of remaining each part iHas approximately (r C, i(t 2i-t 2i-1)+r B, i(t 2i-t 2i-1)+r A, i(t 2i-t 2i-1))/(C 0+ ∑ r C, i(t 2i-t 2i-1)+B 0+ ∑ r B, I(t 2i-t 2i-1)+A 0+ ∑ r A, 1(t 2i-t 2i-1)) molar fraction, this each part has approximately from M (1+ ∑ X i+ ∑ Y i-X i) to M (1+ ∑ X i+ ∑ Y i) molecular-weight average that separates, wherein:
X i=R 0∫ ((C 0+ B 0+ A 0)/(C 0+ B 0+ A 0+ (r A, i+ r B, i+ r C, i) (t-t 2i-1))) dt, wherein t is from t 2i-1To t 2i, Y i=R 0((C 0+ B 0+ A 0)/(C 0+ B 0+ A 0+ (r A, i+ r B, i+ r C, i) (t-t 2i-1))) (t 2i+1-t 2i).
Therefore, be to be understood that embodiment of the present invention disclosed herein only are used to illustrate principle of the present invention.The detailed content of illustrational embodiment be not limited to the scope of claim, it is important that its own described feature is considered to the present invention.

Claims (36)

1. method for preparing polyaddition reaction product with predetermined molecular weight distribution, this method may further comprise the steps:
A) starting condition of definite reaction;
B) utilize at least one velocity constant of reacting, calculate at least a add-on that will add at least a reactive component in the reaction at least one reaction times after the reaction initiation time;
C) the initiation time with the starting condition initiation reaction; With
D) in the reaction times, add reactive component in reaction;
Wherein, described reactive component is selected from:
A) at least a catalyzer;
B) at least a promotor;
C) at least a reversible chain-transfer agent; With
, b) and arbitrary combination c) d) a).
2. the process of claim 1 wherein that described catalyzer comprises at least a following metal-based catalyst that is selected from:
A) aluminium-based catalyst;
B) manganese-based catalyst;
C) chromium-based catalysts;
D) cobalt-base catalyst;
E) yttrium is catalyst based;
F) zinc-base catalyzer;
G) cadmium is catalyst based;
H) nickel-base catalyst;
I) from a) to h) arbitrary combination.
3. claim 1 or 2 method, the reaction product of wherein said addition polymerization is a polycarbonate.
4. the method for one of claim 1-3, wherein said addition polymerization is the copolymerization of carbonic acid gas and epoxide.
5. the method for one of claim 1-4, wherein said addition polymerization is the copolymerization of carbonic acid gas and propylene oxide.
6. the method for one of claim 1-5, it further comprises when making this reaction terminating, adds chain terminator before the termination time.
7. the method for one of claim 1-6 wherein adds described reactive component in the described reaction in one or more discontinuous steps.
8. the method for one of claim 1-7 wherein adds described reactive component in a single step, makes that the molecular weight distribution of product is a bimodal distribution.
9. the method for one of claim 1-7 wherein adds described reactive component in two steps, makes that the molecular weight distribution of product is that three peaks distribute.
10. the method for one of claim 1-6 wherein adds the speed of described reactive component with continuous interpolation in the described reaction continuously.
11. product that makes by the method for one of claim 1-10.
12. a method of controlling the molecular weight distribution of polyaddition reaction product, this method may further comprise the steps:
A) cause polyaddition reaction in the initiation time; With
B) at least one reaction times after the initiation time at least a reactive component is added in the reaction;
Wherein said reactive component is selected from:
A) at least a catalyzer;
B) at least a promotor;
C) at least a reversible chain-transfer agent; With
, b) and arbitrary combination c) d) a).
13. the method for claim 12, wherein said catalyzer comprise at least a following metal-based catalyst that is selected from:
A) aluminium-based catalyst;
B) manganese-based catalyst;
C) chromium-based catalysts;
D) cobalt-base catalyst;
E) yttrium is catalyst based;
F) zinc-base catalyzer;
G) cadmium is catalyst based;
H) nickel-base catalyst;
I) from a) to h) arbitrary combination.
14. the method for claim 12 or 13, the reaction product of wherein said addition polymerization is a polycarbonate.
15. the method for one of claim 12-14, wherein said addition polymerization are the copolymerizations of carbonic acid gas and epoxide.
16. the method for one of claim 12-15, wherein said addition polymerization are the copolymerizations of carbonic acid gas and propylene oxide.
17. the method for one of claim 12-16, it further comprises when with reaction terminating, adds chain terminator before the termination time.
18. the method for one of claim 12-17 wherein adds described reactive component in the described reaction in one or more discontinuous steps.
19. the method for one of claim 12-18 wherein adds described reactive component in a single step, make that the molecular weight distribution of product is a bimodal distribution.
20. the method for one of claim 12-18 wherein adds described reactive component in two steps, make that the molecular weight distribution of product is that three peaks distribute.
21. the method for one of claim 12-17 wherein adds the speed of described reactive component with continuous interpolation in the described reaction continuously.
22. the method for claim 21, the speed time to time change of wherein said continuous interpolation.
23. product that makes by the method for one of claim 12-22.
24. the method for the molecular weight distribution of a polycarbonate products of controlling polyaddition reaction, this method may further comprise the steps:
A) cause polyaddition reaction in the initiation time; With
B) at least one reaction times after the initiation time at least a reactive component is added in the reaction.
25. the method for claim 24, wherein said reactive component is selected from following:
A) at least a catalyzer;
B) at least a promotor;
C) at least a chain-transfer agent; With
, b) and arbitrary combination c) d) a).
26. the method for claim 24 or 25, wherein said catalyzer comprise at least a following metal-based catalyst that is selected from:
A) aluminium-based catalyst;
B) manganese-based catalyst;
C) chromium-based catalysts;
D) cobalt-base catalyst;
E) yttrium is catalyst based;
F) zinc-base catalyzer;
G) cadmium is catalyst based;
H) nickel-base catalyst;
I) from a) to h) arbitrary combination.
27. the method for one of claim 24-26, wherein said addition polymerization are the copolymerizations of carbonic acid gas and epoxide.
28. the method for one of claim 24-27, wherein said addition polymerization are the copolymerizations of carbonic acid gas and propylene oxide.
29. the method for one of claim 24-28 wherein adds described reactive component in the described reaction in one or more discontinuous steps.
30. the method for one of claim 24-29 wherein adds described reactive component in a single step, make that the molecular weight distribution of product is a bimodal distribution.
31. the method for one of claim 24-29 wherein adds described reactive component in two steps, make that the molecular weight distribution of product is that three peaks distribute.
32. the method for one of claim 24-28 wherein adds the speed of described reactive component with continuous interpolation in the described reaction continuously.
33. the method for claim 32, the speed time to time change of wherein said continuous interpolation.
34. product that makes by the method for one of claim 24-33.
35. polymeric articles that comprises the first addition polymer product of single batchwise polymerization, the wherein said first addition polymer product has the molecular weight distribution that is different from the second addition polymer product, and the described second addition polymer product is to produce by the total overall reaction component that adds the second addition polymer product when the polyreaction of preparation second addition polymer begins or finishes.
36. the polymeric articles of claim 35, the wherein said first addition polymer product is a carbonate polymer.
CN200980119858.7A 2008-05-29 2009-05-27 Methods of controlling molecular weight distribution of polymers and compositions thereof Active CN102046695B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310308300.1A CN103626983B (en) 2008-05-29 2009-05-27 The method controlling polymer and combinations thereof thing molecular weight distribution

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US12/129,106 US7858729B2 (en) 2008-05-29 2008-05-29 Methods of controlling molecular weight distribution of polymers and compositions thereof
US12/129,106 2008-05-29
PCT/US2009/045216 WO2009148889A2 (en) 2008-05-29 2009-05-27 Methods of controlling molecular weight distribution of polymers and compositions thereof

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201310308300.1A Division CN103626983B (en) 2008-05-29 2009-05-27 The method controlling polymer and combinations thereof thing molecular weight distribution

Publications (2)

Publication Number Publication Date
CN102046695A true CN102046695A (en) 2011-05-04
CN102046695B CN102046695B (en) 2013-08-21

Family

ID=41380619

Family Applications (2)

Application Number Title Priority Date Filing Date
CN200980119858.7A Active CN102046695B (en) 2008-05-29 2009-05-27 Methods of controlling molecular weight distribution of polymers and compositions thereof
CN201310308300.1A Active CN103626983B (en) 2008-05-29 2009-05-27 The method controlling polymer and combinations thereof thing molecular weight distribution

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201310308300.1A Active CN103626983B (en) 2008-05-29 2009-05-27 The method controlling polymer and combinations thereof thing molecular weight distribution

Country Status (13)

Country Link
US (2) US7858729B2 (en)
EP (1) EP2281013B1 (en)
JP (1) JP5552116B2 (en)
KR (2) KR101825340B1 (en)
CN (2) CN102046695B (en)
DK (1) DK2281013T3 (en)
ES (1) ES2663704T3 (en)
HU (1) HUE038560T2 (en)
NO (1) NO2281013T3 (en)
PL (1) PL2281013T3 (en)
PT (1) PT2281013T (en)
TR (1) TR201802600T4 (en)
WO (1) WO2009148889A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104718236A (en) * 2012-06-27 2015-06-17 诺沃梅尔公司 Catalysts and methods for polyester production

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7858729B2 (en) * 2008-05-29 2010-12-28 Novomer, Inc. Methods of controlling molecular weight distribution of polymers and compositions thereof
CN102164987B (en) 2008-08-22 2015-07-08 诺沃梅尔公司 Catalysts and methods for polymer synthesis
KR101913673B1 (en) 2008-09-08 2018-11-01 사우디 아람코 테크놀로지스 컴퍼니 Polycarbonate polyol compositions
KR102028314B1 (en) * 2008-09-17 2019-10-07 사우디 아람코 테크놀로지스 컴퍼니 Purification of polycarbonates
KR101486483B1 (en) * 2010-04-13 2015-01-27 에스케이이노베이션 주식회사 Block and graft copolymers of poly(alkylene carbonate) and various polymers
US11644471B2 (en) 2010-09-30 2023-05-09 Ablynx N.V. Techniques for predicting, detecting and reducing aspecific protein interference in assays involving immunoglobulin single variable domains
CN103221454A (en) 2010-11-23 2013-07-24 帝斯曼知识产权资产管理有限公司 Polycarbonate polyol compositions
JP6134882B2 (en) 2010-11-23 2017-05-31 ノボマー， インコーポレイテッド Polycarbonate polyol composition
KR101406989B1 (en) * 2011-01-18 2014-06-13 에스케이이노베이션 주식회사 Multilayer film
US9327280B2 (en) 2011-05-13 2016-05-03 Novomer, Inc. Catalytic carbonylation catalysts and methods
IL250396B (en) 2011-06-23 2022-06-01 Ablynx Nv Techniques for predicting, detecting and reducing aspecific protein interference in assays involving immunoglobulin single variable domains
CN104428370A (en) 2012-04-16 2015-03-18 诺沃梅尔公司 Adhesive compositions and methods
US9388277B2 (en) 2012-05-24 2016-07-12 Novomer, Inc. Polycarbonate polyol compositions and methods
WO2014031811A1 (en) 2012-08-24 2014-02-27 Novomer, Inc. Metal complexes
US9738760B2 (en) 2013-05-01 2017-08-22 Novomer, Inc. Aliphatic polycarbonate compositions and methods
WO2015154001A1 (en) 2014-04-03 2015-10-08 Novomer, Inc. Aliphatic polycarbonate polyol compositions
WO2015171372A1 (en) 2014-05-05 2015-11-12 Novomer, Inc. Catalyst recycle methods
US10597294B2 (en) 2014-05-30 2020-03-24 Novomer, Inc. Integrated methods for chemical synthesis
WO2016015019A1 (en) 2014-07-25 2016-01-28 Novomer, Inc. Synthesis of metal complexes and uses thereof
MA41510A (en) 2015-02-13 2017-12-19 Novomer Inc ACRYLIC ACID PRODUCTION PROCESS
MA41513A (en) 2015-02-13 2017-12-19 Novomer Inc DISTILLATION PROCESS FOR ACRYLIC ACID PRODUCTION
WO2016130998A1 (en) 2015-02-13 2016-08-18 Novomer, Inc. Continuous carbonylation processes
MA41514A (en) 2015-02-13 2017-12-19 Novomer Inc INTEGRATED CHEMICAL SYNTHESIS PROCESSES
WO2019126221A1 (en) 2017-12-22 2019-06-27 Saudi Aramco Technologies Company Catalysts for polycarbonate production
EP3781609A1 (en) 2018-04-18 2021-02-24 Saudi Aramco Technologies Company End-group isomerization of poly(alkylene carbonate) polymers
US11180609B2 (en) 2018-08-02 2021-11-23 Saudi Aramco Technologies Company Sustainable polymer compositions and methods
EP3856820A1 (en) 2018-09-24 2021-08-04 Saudi Aramco Technologies Company Polycarbonate block copolymers and methods thereof
CN113265018B (en) * 2021-06-04 2022-03-29 大连理工大学 Polymer molecular weight distribution regulation and control method based on locking-unlocking mechanism

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070059621A (en) * 2005-12-07 2007-06-12 주식회사 엘지화학 Preparation of polyolefin using magnesium supported ziegler-natta catalysts
WO2007067965A2 (en) * 2005-12-09 2007-06-14 Dow Global Technologies Inc. Processes of controlling molecular weight distribution in ethylene/alpha-olefin compositions

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248415A (en) * 1963-01-16 1966-04-26 Pittsburgh Plate Glass Co Method of preparing high molecular weight polycarbonates
US3585168A (en) * 1968-09-21 1971-06-15 Shohei Inoue Process for producing copolymer of epoxide and carbon dioxide
US3953383A (en) * 1972-07-21 1976-04-27 Nippon Oil Seal Industry Co., Ltd. Catalytic process for copolymerizing epoxy compounds with carbon dioxide
US3900424A (en) * 1972-07-21 1975-08-19 Nippon Oil Seal Ind Co Ltd Catalyst for copolymerizing epoxy compounds with carbon dioxide
JPS57126809A (en) * 1981-01-30 1982-08-06 Sumitomo Chem Co Ltd Ethylene/alpha-olefin copolymer
US4686276A (en) * 1985-12-30 1987-08-11 The Dow Chemical Company Process for preparing poly (alkylene carbonates)
US4665136A (en) * 1986-04-07 1987-05-12 Air Products And Chemicals, Inc. Process for producing novel block alkylene polycarbonate copolymers
JPH04106104A (en) * 1990-08-27 1992-04-08 Nippon Zeon Co Ltd Process and apparatus for controlling reaction in polymerization step
FI924730A (en) 1992-03-20 1993-09-21 Rohm & Haas PROTECTION OF POLYMERS
US6133402A (en) * 1998-08-04 2000-10-17 Cornell Research Foundation, Inc. Polycarbonates made using high activity catalysts
US6486271B1 (en) 2001-03-09 2002-11-26 Fina Technology, Inc. Method of controlling molecular weight distributions during a polymerization process
JP3943382B2 (en) * 2001-12-10 2007-07-11 日本合成化学工業株式会社 Polyvinyl alcohol resin and use thereof
US7304172B2 (en) * 2004-10-08 2007-12-04 Cornell Research Foundation, Inc. Polycarbonates made using highly selective catalysts
JP4590284B2 (en) * 2005-03-01 2010-12-01 学校法人東京理科大学 Method for producing polycarbonate
JP2008045069A (en) * 2006-08-18 2008-02-28 Jsr Corp Cyclic olefin-based addition copolymer, method for producing the same, and application thereof
EP2112187A1 (en) 2008-04-21 2009-10-28 Stichting Dutch Polymer Institute Process for the preparation of polycarbonates
GB0807607D0 (en) 2008-04-25 2008-06-04 Imp Innovations Ltd Catalyst
US7858729B2 (en) * 2008-05-29 2010-12-28 Novomer, Inc. Methods of controlling molecular weight distribution of polymers and compositions thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070059621A (en) * 2005-12-07 2007-06-12 주식회사 엘지화학 Preparation of polyolefin using magnesium supported ziegler-natta catalysts
WO2007067965A2 (en) * 2005-12-09 2007-06-14 Dow Global Technologies Inc. Processes of controlling molecular weight distribution in ethylene/alpha-olefin compositions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104718236A (en) * 2012-06-27 2015-06-17 诺沃梅尔公司 Catalysts and methods for polyester production

Also Published As

Publication number Publication date
HUE038560T2 (en) 2018-10-29
US8324337B2 (en) 2012-12-04
KR101979576B1 (en) 2019-05-17
PT2281013T (en) 2018-03-28
DK2281013T3 (en) 2018-03-05
WO2009148889A3 (en) 2010-02-25
US20110065894A1 (en) 2011-03-17
JP5552116B2 (en) 2014-07-16
EP2281013B1 (en) 2017-12-27
KR20180014844A (en) 2018-02-09
ES2663704T3 (en) 2018-04-16
US7858729B2 (en) 2010-12-28
KR101825340B1 (en) 2018-02-05
KR20110013493A (en) 2011-02-09
WO2009148889A2 (en) 2009-12-10
EP2281013A2 (en) 2011-02-09
EP2281013A4 (en) 2015-04-29
CN103626983A (en) 2014-03-12
TR201802600T4 (en) 2018-03-21
NO2281013T3 (en) 2018-05-26
JP2011522091A (en) 2011-07-28
US20090299032A1 (en) 2009-12-03
PL2281013T3 (en) 2018-06-29
CN103626983B (en) 2016-12-28
CN102046695B (en) 2013-08-21

Similar Documents

Publication Publication Date Title
CN102046695B (en) Methods of controlling molecular weight distribution of polymers and compositions thereof
CN101379091B (en) Polymerization process with catalyst reactivation
Aoshima et al. Interconvertible living radical and cationic polymerization through reversible activation of dormant species with dual activity
CN104080851B (en) There is low-density based on ethylene the polymer of wide molecular weight distribution and low extractable
CN103626982B (en) A kind of method improving the melt strength of polyester resin
JP2008504404A (en) Branched polylactic acid polymer and its production method
CN101090934B (en) Extruded propylene resin foam
KR20140041162A (en) Method for preparing polyolfin and polyolefin prepared therefrom
CN113248642A (en) Method for preparing polyolefin elastomer based on microchannel reactor technology and product
CN109438689B (en) Propylene oxide-carbon dioxide copolymer and preparation method thereof
CN101253205B (en) Process for narrowing short-chain branching distribution in two-step ethylene polymerizations and products
CN103804551B (en) A kind of preparation method of ethylene copolymer
CN102504113A (en) Long-branched polyethylene resin and preparation method thereof
CN106928394A (en) Thermoplastic resin composition and molded article formed therefrom
US11773198B2 (en) Polyolefin process monitoring and control
Zaldívar et al. On the preparation of acrylic acid/vinyl acetate copolymers with constant composition: 4. Modelling batch and continuous free-radical AA/VA copolymerization
CN107722160A (en) A kind of copolymer of 2 hydroxymethyl acrylate and styrene and preparation method thereof
Ciardelli et al. Synthesis of Polymers for Plastic Materials
Voyer et al. Polymerization of optically active β‐substituted β‐propiolactones. IV. β‐1, 1‐dichloroalkyl β‐propiolactones polymerized with aluminum triisopropoxide
Koltzenburg et al. Copolymerization
Gedde et al. Polymer Synthesis
Ye et al. Metal-Free Lewis Pair Catalysts for a One-Pot Terpolymerization of Propylene Oxide, ʟ-Lactide and CO2
Dube A systematic approach to the study of multicomponent polymerization kinetics.
JPS5813605A (en) Preparation of ethylenic copolymer
JPH0517578A (en) Compound of polymer

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20171229

Address after: Saudi Aramco

Patentee after: Saudi Aram technology company

Address before: American New York

Patentee before: Novomer Inc.

TR01 Transfer of patent right